Infrared spectra and molecular dynamics simulations of cis-HONO isomer in an argon matrix

Talik, Tadeusz; Tokhadze, K. G.; Mielke, Zofia

doi:10.1016/s0022-2860(02)00071-6

Cited by 4 publications

(2 citation statements)

References 16 publications

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“…As shown in Table 3, interestingly, the gas phase calculations show that the TiH 2 scissor and wag frequencies are nearly degenerate (612.4 vs. 613.9 cm -1 ) while the argon matrix calculations indicate that the two frequencies are just like a doublet (594.1 vs. 600.1 cm -1 ). This point should be paid more attention to during the assignment of the experimental frequencies since the doublets may be easily explained to be due to the matrix site effect [4,9,10,34]. Note that the experimental argon matrix frequency 588.5 cm -1 was only assigned to the TiH 2 wag mode of their calculation (616.8 cm -1 ) [3].…”

Section: Resultsmentioning

confidence: 98%

Theoretical studies on the infrared spectrum of the tetrahedral molecules R2MH2 (R = D(H), CH3, OH; M = Ti, Zr, Hf)

Liu

Zhao

2008

Struct Chem

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Using Stuttgart/Dresden effective core potentials MWB28, MWB60, and GTO valence basis sets (8s7p6d)/[6s5p3d], (8s7p6d)/[6s5p3d] for Zr and Hf atoms and 6-311++G(3df,3pd) basis set for C, H, O, and Ti atoms, tight convergence criteria geometry optimizations and harmonic frequency calculations are performed at B3LYP and B3LYP/IEF-PCM levels of theory so as to model the gas phase and argon matrix infrared spectra of the tetrahedral molecules R 2 MH 2 (R = D(H), CH 3 , OH; M = Ti, Zr, Hf). Influence of the transition metal and/or substituent group on the symmetric and asymmetric stretching frequencies of the MH 2 fragment of the R 2 MH 2 molecules is investigated at both the levels of theory. The modelling of the argon matrix effect improves the agreement between the calculated frequencies and the experimental ones. The calculated argon matrix to gas phase frequency shifts is compared reasonably to the experimental argon to neon matrix shifts.

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Section: Resultsmentioning

confidence: 98%

Theoretical studies on the infrared spectrum of the tetrahedral molecules R2MH2 (R = D(H), CH3, OH; M = Ti, Zr, Hf)

Liu

Zhao

2008

Struct Chem

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“…In later years, different molecular dynamics methods were devised to simulate the effect of matrix sites on the guest molecule [27,28]. Such simulations were used to reproduce matrix shifts in specific molecules and molecular complexes such as HONO and the formic acid dimer [29,30]. In their work on the acetylene molecule, Jose et al [31] carried out electronic structure calculations for acetylene-argon and acetylene-nitrogen complexes to determine if the matrix shifts of the asymmetric C-H stretch ν 3 in argon and nitrogen matrices could be reproduced.…”

Section: Introductionmentioning

confidence: 99%

Confinement effects on C–H and C–F stretching vibrational frequencies of difluoromethane in cold inert gas matrixes: a combined infrared spectroscopy and electronic structure theory study

Banerjee

Chakraborty

2021

Eur. Phys. J. D

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Mid-infrared spectra of difluoromethane (DFM) have been recorded by confining the molecule in the matrix cages of pure argon, nitrogen and in the mixed matrixes of argon and nitrogen obtained by mixing the two gases in definite proportions. The measured spectra depict distinct confinement effects in terms of the infrared spectral shifts of the C-H and C-F stretching vibrational fundamentals as compared to the free molecules in the gas-phase, and also some remarkable changes in band appearances and relative intensities. The signs of the spectral shifts are observed to be different for the νC-H and νC-F transitions. Pronounced blue shifts are observed for the two νC-H modes in pure nitrogen matrix, which progressively reduce in magnitude in the mixed matrixes, and is least in the pure argon matrix. On the other hand, distinct red shifts of the νC-F vibrations are evident in pure nitrogen matrix, which are reduced in magnitude in the mixed matrixes, and become even less pronounced in pure argon matrix. The effect of Fermi resonances in the νC-H region, that has motivated several previous investigations of DFM including high resolution gas phase studies, becomes explicit upon comparison of the matrix isolation spectrum with the gas phase spectrum. Electronic structure calculations using several DFT and DFT-D methods, in conjunction with NBO analysis, have been carried out for various sizes of DFM-N2 and DFM-Ar complexes in order to understand the underlying interactions responsible for the observed shifts. The calculations are found to satisfactorily reproduce the observed variations in magnitude and direction of the shifts of both the νC-H and νC-F transitions for the change of the medium. It is inferred that the inert gas matrix environment exerts an electronic re-organization within the DFM molecule, and the consequent rehybridization of the carbon-centric hybrid orbital of the C-H and C-F bonds is responsible for the observed spectral shifts.

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Applications in Inorganic Chemistry

Nakamoto

2008

Infrared and Raman Spectra of Inorganic and Coordination Compounds

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Infrared spectra and molecular dynamics simulations of cis-HONO isomer in an argon matrix

Cited by 4 publications

References 16 publications

Theoretical studies on the infrared spectrum of the tetrahedral molecules R2MH2 (R = D(H), CH3, OH; M = Ti, Zr, Hf)

Theoretical studies on the infrared spectrum of the tetrahedral molecules R2MH2 (R = D(H), CH3, OH; M = Ti, Zr, Hf)

Confinement effects on C–H and C–F stretching vibrational frequencies of difluoromethane in cold inert gas matrixes: a combined infrared spectroscopy and electronic structure theory study

Applications in Inorganic Chemistry

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